Journal :   Asian Journal of Research in Chemistry

Volume No. :   7

Issue No. :  3

Year :  2014

Pages :   379-385

ISSN Print :  0974-4169

ISSN Online :  0974-4150


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Kinetics and Mechanism of HgCl2 Catalysed Oxidation of Organic Sulfides by Permanganate in Non-Aqueous Medium



Address:   K.P. Srivastava* and Sanjay Kumar Rai
P.G. Department of Chemistry, Ganga Singh College, Jai Prakash University, Chapra-841 301 Bihar, India
*Corresponding Author
DOI No:

ABSTRACT:
The rates of mercuric chloride (Lewis acid) catalysed oxidation of thioanisole and several para-substituted thioanisoles by permanganate have been studied in anhydrous acetone solutions. The kinetic rate law obtained indicates that a complex between permanganate and the Lewis acid (HgCl2) is formed before oxidation of the sulfur-containing compounds occurs. The function of the mercuric chloride is to enhance the reactivity of permanganate. A Hammett ? value of -0.60 ±0.04 is obtained for the oxidation of sulfides at 23.0 0C. A negative ? value means that the sulfur is electron deficient in the transition state. Values for the HOMO energies of sulfides and the LUMO energies for permanganate ion and the permanganate-mercuric chloride complex have been calculated. The results indicate that electron donating substituents on the ring increase the rate of the reaction and electron withdrawing groups slow down the reaction.
KEYWORDS:
Thioanisoles, permanganate, Mercuric chloride, acid catalysedoxidation, LUMO, HOMO.
Cite:
K.P. Srivastava, Sanjay Kumar Rai. Kinetics and Mechanism of HgCl2 Catalysed Oxidation of Organic Sulfides by Permanganate in Non-Aqueous Medium. Asian J. Research Chem. 7(4): April 2014; Page 379-385.
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